Nitrogen-Rich Molybdenum Nitride Synthesized in a Crucible under Air.

The triple bond in N2 is significantly stronger than the double bond in O2, meaning that synthesizing nitrogen-rich nitrides typically requires activated nitrogen precursors, such as ammonia, plasma-cracked atomic nitrogen, or high-pressure N2. Here, we report a synthesis of nitrogen-rich nitrides under ambient pressure and atmosphere. Using Na2MoO4 and dicyandiamide precursors, we synthesized nitrogen-rich γ-Mo2N3 in an alumina crucible under an ambient atmosphere, heated in a box furnace between 500 and 600 °C. Byproducts of this metathesis reaction include volatile gases and solid Na(OCN), which can be washed away with water. X-ray diffraction and neutron diffraction showed Mo2N3 with a rock salt structure having cation vacancies, with no oxygen incorporation, in contrast to the more common nitrogen-poor rock salt Mo2N with anion vacancies. Moreover, an increase in temperature to 700 °C resulted in molybdenum oxynitride, Mo0.84N0.72O0.27. This work illustrates the potential for dicyandiamide as an ambient-temperature metathesis precursor for an increased effective nitrogen chemical potential under ambient conditions. The classical experimental setting often used for solid-state oxide synthesis, therefore, has the potential to expand the nitride chemistry.

Nickel Carbide Nanoparticle Catalyst for Selective Hydrogenation of Nitriles to Primary Amines.

Despite its unique physicochemical properties, the catalytic application of nickel carbide (Ni3 C) in organic synthesis is rare. In this study, we report well-defined nanocrystalline Ni3 C (nano-Ni3 C) as a highly active catalyst for the selective hydrogenation of nitriles to primary amines. The activity of the aluminum-oxide-supported nano-Ni3 C (nano-Ni3 C/Al2 O3 ) catalyst surpasses that of Ni nanoparticles. Various aromatic and aliphatic nitriles and dinitriles were successfully converted to the corresponding primary amines under mild conditions (1 bar H2 pressure). Furthermore, the nano-Ni3 C/Al2 O3 catalyst was reusable and applicable to gram-scale experiments. Density functional theory calculations suggest the formation of polar hydrogen species on the nano-Ni3 C surface, which were attributed to the high activity of nano-Ni3 C towards nitrile hydrogenation. This study demonstrates the utility of metal carbides as a new class of catalysts for liquid-phase organic reactions.

Low-Temperature Chiral Crystal Structure and Superconductivity in (Pt0.2Ir0.8)3Zr5.

We report the observation of superconductivity in (Pt0.2Ir0.8)3Zr5 with a chiral space group (P6122) at low temperatures. The bulk nature of the superconductivity at a transition temperature of 2.2 K was confirmed using specific heat measurements. We revealed that (Pt0.2Ir0.8)3Zr5 obeys the weak-coupling Bardeen-Cooper-Schrieffer model, and the dominant mechanism in the upper critical field is the orbital pair-breaking limit rather than the Pauli-Clogston limit. This indicates that the antisymmetric spin-orbit coupling caused by the chiral crystal structure does not significantly affect the superconductivity of (Pt0.2Ir0.8)3Zr5.

Observation of superconductivity and enhanced upper critical field of η-carbide-type oxide Zr4Pd2O.

We report the first observation of bulk superconductivity of a η-carbide-type oxide Zr4Pd2O. The crystal structure and the superconducting properties were studied through synchrotron X-ray diffraction, magnetization, electrical resistivity, and specific heat measurement. The superconducting transition was observed at Tc = 2.73 K. Our measurement revealed that the η-carbide-type oxide superconductor Zr4Pd2O shows an enhanced upper critical field µ0Hc2(0) = 6.72 T, which violates the Pauli-Clogston limit µ0HP = 5.29 T. On the other hand, we found that the enhanced upper critical field is absent in a Rh analogue Zr4Rh2O. The large µ0Hc2(0) of Zr4Pd2O would be raised from strong spin-orbit coupling with Pd-4d electrons. The discovery of new superconducting properties for Zr4Pd2O would shed light on the further development of η-carbide-type oxide superconductors.

Fe Site Order and Magnetic Properties of Fe1/4NbS2.

Transition-metal dichalcogenides (TMDs) have long been attractive to researchers for their diverse properties and high degree of tunability. Most recently, interest in magnetically intercalated TMDs has resurged due to their potential applications in spintronic devices. While certain compositions featuring the absence of inversion symmetry such as Fe1/3NbS2 and Cr1/3NbS2 have garnered the most attention, the diverse compositional space afforded through the host matrix composition as well as intercalant identity and concentration is large and remains relatively underexplored. Here, we report the magnetic ground state of Fe1/4NbS2 that was determined from low-temperature neutron powder diffraction as an A-type antiferromagnet. Despite the presence of overall inversion symmetry, the pristine compound manifests spin polarization induced by the antiferromagnetic order at generic k points, based on density functional theory band-structure calculations. Furthermore, by combining synchrotron diffraction, pair distribution function, and magnetic susceptibility measurements, we find that the magnetic properties of Fe1/4NbS2 are sensitive to the Fe site order, which can be tuned via electrochemical lithiation and thermal history.

High-glycemic index meal acutely potentiates blood pressure response to static handgrip exercise in healthy humans.

Blood glucose levels acutely increase postprandially depending on the type of meal consumed. However, it remains unclear whether postprandial hyperglycemia temporally affects cardiovascular responses to static handgrip exercise (SHG-ex). Thus, this study aimed to examine whether increased blood glucose induced by consumption of a high-glycemic index (HGI) meal affects pressor response to SHG-ex. A total of 14 healthy participants (7 women and 7 men) consumed an HGI meal, a low-glycemic index (LGI) meal, or no meal (control). Participants performed 30% maximal voluntary contraction SHG-ex followed by a postexercise muscle ischemia (PEMI) test before the meal and 60 min after consuming the meal. Blood glucose, plasma insulin, and plasma triglyceride levels were measured, and the area under the curve until 60 min (AUC0-60 min) after meal consumption was calculated. The HGI and LGI groups showed higher blood glucose and insulin AUC0-60 min than the control group (P < 0.001). At 60 min after the meal, the changes in blood pressure during SHG-ex were significantly greater in the HGI group, but not in the LGI group, than in the control group. The changes in blood pressure at the onset and end of SHG-ex 60 min after the meal were positively correlated with blood glucose AUC0-60 min (r = 0.321, P = 0.038; r = 0.402, P = 0.008, respectively) and plasma insulin AUC0-60 min (r = 0.339, P = 0.028; r = 0.302, P = 0.052, respectively). However, no association was observed during PEMI. These data suggest that postprandial hyperglycemia and hyperinsulinemia acutely exaggerate pressor response during SHG-ex in healthy young adults.NEW & NOTEWORTHY Postprandial hyperglycemia following consumption of a high-glycemic index (HGI) meal potentiated blood pressure response to static handgrip exercise (SHG-ex) in healthy young adults. These findings provide important insight into the role of the diet on acute circulatory response to exercise in healthy adults.

Synthesis of lithium oxy-thiophosphate solid electrolytes with Li10GeP2S12 structure by a liquid phase process using 2-propanol.

Lithium oxy-thiophosphates isostructural with Li10GeP2S12 (LGPS) were synthesized by a liquid-phase process using 2-propanol as the solvent and Li2S and P2S5 as the starting materials. The XRD and 31P NMR results indicate that the synthesized compound has a slightly shrieked LGPS-type crystal structure where sulfur in PS43- is partially replaced by oxygen. The sample synthesized from the nominal composition of Li2S : P2S5 = 2.5 : 1 and at the annealing temperature of 300 °C exhibited the ionic conductivity of 1.6 × 10-4 S cm-1 at 25 °C. The synthesized solid electrolyte was found to be electrochemically stable in the potential range of 0-5 V, and also relatively stable under air with low relative humidity.

Synthesis and Characterization of a Trigonal Layered Compound AgInS2.

Depending on thermal and pressure conditions, AgInS2 exhibits various crystal structures. In this study, we synthesized a high-purity polycrystalline sample of trigonal AgInS2, which is a layered compound, using a high-pressure synthesis technique. The crystal structure was investigated by synchrotron powder X-ray diffraction and the Rietveld refinement. On the basis of band calculation, X-ray photoelectron spectroscopy, and electrical resistance measurements, we found that the obtained trigonal AgInS2 is a semiconductor. Temperature dependencies of electrical resistance of AgInS2 were measured by a diamond anvil cell up to 31.2 GPa. Although semiconducting behavior was suppressed with pressure, metallic behavior was not observed within the pressure range investigated in this study.

Highly active and stable surface structure for oxygen evolution reaction originating from balanced dissolution and strong connectivity in BaIrO3 solid solutions.

Catalysts for the oxygen evolution reaction (OER) are receiving great interest since OER remains the bottleneck of water electrolyzers for hydrogen production. Especially, OER in acidic solutions is crucial since it produces high current densities and avoids precipitation of carbonates. However, even the acid stable iridates undergo severe dissolution during the OER. BaIrO3 has the strongest IrO6 connectivity and stable surface structure, yet it suffers from lattice collapse after OER cycling, making it difficult to improve the OER durability. In the present study, we have successfully developed an OER catalyst with both high intrinsic activity and stability under acidic conditions by preventing the lattice collapse after repeated OER cycling. Specifically, we find that the substitution of Ir-site with Mn for BaIrO3 in combination with OER cycling leads to a remarkable activity enhancement by a factor of 28 and an overall improvement in stability. This dual enhancement of OER performance was accomplished by the novel strategy of slightly increasing the Ir-dissolution and balancing the elemental dissolution in BaIr1-x Mn x O3 to reconstruct a rigid surface with BaIrO3-type structure. More importantly, the mass activity for BaIr0.8Mn0.2O3 reached ∼73 times of that for IrO2, making it a sustainable and promising OER catalyst for energy conversion technologies.

Investigation of Superconductivity in Ce-Doped (La,Pr)OBiS2 Single Crystals.

Single crystals of Ce-doped (La,Pr)OBiS2 superconductors, the multinary rare-earth elements substituted ROBiS2, were successfully grown. The grown crystals typically had a size of 1-2 mm and a plate-like shape with a well-developed c-plane. The c-axis lattice constants of the obtained (La,Ce,Pr)OBiS2 single crystals were approximately 13.6-13.7 Å, and the superconducting transition temperature was 1.23-2.18 K. Valence fluctuations of Ce and Pr were detected through X-ray absorption spectroscopy analysis. In contrast to (Ce,Pr)OBiS2 and (La,Ce)OBiS2, the superconducting transition temperature of (La,Ce,Pr)OBiS2 increased with the increasing concentrations of the tetravalent state at the R-site.

Synthesis and Characterization of High-Entropy-Alloy-Type Layered Telluride MBi2Te4 (M = Ag, In, Sn, Pb, Bi).

Recently, high-entropy alloys (HEAs) and HEA-type compounds have been extensively studied in the fields of material science and engineering. In this article, we report on the synthesis of a layered system MBi2Te4 where the M site possesses low-, middle-, and high-entropy states. The samples with M = Pb, Ag1/3Pb1/3Bi1/3, and Ag1/5In1/5Sn1/5Pb1/5Bi1/5 were newly synthesized and the crystal structure was examined by synchrotron X-ray diffraction and Rietveld refinement. We found that the M-Te2 distance was systematically compressed with decreasing lattice constants, where the configurational entropy of mixing at the M site is also systematically increased. The details of structural refinements and the electrical transport property are presented.

Sodium bicarbonate ingestion mitigates the heat-induced hyperventilation and reduction in cerebral blood velocity during exercise in the heat.

Hyperthermia during exercise in the heat causes minute ventilation ([Formula: see text]) to increase, which leads to reductions in arterial CO2 partial pressure ([Formula: see text]) and cerebral blood flow. On the other hand, sodium bicarbonate ingestion reportedly results in metabolic alkalosis, leading to decreased [Formula: see text] and increased [Formula: see text] during prolonged exercise in a thermoneutral environment. Here, we investigated whether sodium bicarbonate ingestion suppresses heat-induced hyperventilation and the resultant hypocapnia and cerebral hypoperfusion during prolonged exercise in the heat. Eleven healthy men ingested a solution of sodium bicarbonate (0.3 g/kg body wt) (NaHCO3 trial) or sodium chloride (0.208 g/kg) (NaCl trial). Ninety minutes after the ingestion, the subjects performed a cycle exercise for 60 min at 50% of peak oxygen uptake in the heat (35°C and 40% relative humidity). Esophageal temperature did not differ between the trials throughout (P = 0.56, main effect of trial). [Formula: see text] gradually increased with exercise duration in the NaCl trial, but the increases in [Formula: see text] were attenuated in the NaHCO3 trial (P = 0.01, main effect of trial). Correspondingly, estimated [Formula: see text] and middle cerebral artery blood velocity (an index of anterior cerebral blood flow) were higher in the NaHCO3 than the NaCl trial (P = 0.002 and 0.04, main effects of trial). Ratings of perceived exertion were lower in the NaHCO3 than the NaCl trial (P = 0.02, main effect of trial). These results indicate that sodium bicarbonate ingestion mitigates heat-induced hyperventilation and reductions in [Formula: see text] and cerebral blood velocity during prolonged exercise in the heat.NEW & NOTEWORTHY Hyperthermia causes hyperventilation and concomitant hypocapnia and cerebral hypoperfusion. The cerebral hypoperfusion may underlie central fatigue. We demonstrate that sodium bicarbonate ingestion reduces heat-induced hyperventilation and attenuates hypocapnia-related cerebral hypoperfusion during prolonged exercise in the heat. In addition, we show that sodium bicarbonate ingestion reduces ratings of perceived exertion during the exercise. This study provides new insight into the development of effective strategies for preventing central fatigue during exercise in the heat.

Combustion Reactions between Transition-Metal Chlorides and Sodium Amide and Their Ignition Temperature.

Combustion reactions between metal chlorides and sodium amide proceed in a short time; however, these reactions must be carried out with appropriate safety measures. Investigating their ignition temperatures would facilitate safe handling and give kinetic insights about the reaction between powders. Here, we investigated the products of the reactions between metal chlorides and sodium amide and measured their ignition temperatures. The products were mainly composed of nitrides, metals, and sodium chloride. The reactions of 4d and 5d metal chlorides initiated the reaction below room temperature, while 3d metal chlorides, except copper chloride, initiated the reaction upon heating. We found the correlation between the ignition temperatures and the reaction energies of the combustion reaction.

Kinetically Stabilized Cation Arrangement in Li3 YCl6 Superionic Conductor during Solid-State Reaction.

The main approach for exploring metastable materials is via trial-and-error synthesis, and there is limited understanding of how metastable materials are kinetically stabilized. In this study, a metastable phase superionic conductor, ß-Li3 YCl6 , is discovered through in situ X-ray diffraction after heating a mixture of LiCl and YCl3 powders. While Cl- arrangement is represented as a hexagonal close packed structure in both metastable ß-Li3 YCl6 synthesized below 600 K and stable α-Li3 YCl6 above 600 K, the arrangement of Li+ and Y3+ in ß-Li3 YCl6 determined by neutron diffraction brought about the cell with a 1/√3 a-axis and a similar c-axis of stable α-Li3 YCl6 . Higher Li+ ion conductivity and lower activation energy for Li+ transport are observed in comparison with α-Li3 YCl6 . The computationally calculated low migration barrier of Li+ supports the low activation energy for Li+ conduction, and the calculated high migration barrier of Y3+ kinetically stabilizes this metastable phase by impeding phase transformation to α-Li3 YCl6 . This work shows that the combination of in situ observation of solid-state reactions and computation of the migration energy can facilitate the comprehension of the solid-state reactions allowing kinetic stabilization of metastable materials, and can enable the discovery of new metastable materials in a short time.

Observing and Modeling the Sequential Pairwise Reactions that Drive Solid-State Ceramic Synthesis.

Solid-state synthesis from powder precursors is the primary processing route to advanced multicomponent ceramic materials. Designing reaction conditions and precursors for ceramic synthesis can be a laborious, trial-and-error process, as heterogeneous mixtures of precursors often evolve through a complicated series of reaction intermediates. Here, ab initio thermodynamics is used to model which pair of precursors has the most reactive interface, enabling the understanding and anticipation of which non-equilibrium intermediates form in the early stages of a solid-state reaction. In situ X-ray diffraction and in situ electron microscopy are then used to observe how these initial intermediates influence phase evolution in the synthesis of the classic high-temperature superconductor YBa2 Cu3 O6+ x   (YBCO). The model developed herein rationalizes how the replacement of the traditional BaCO3 precursor with BaO2 redirects phase evolution through a low-temperature eutectic melt, facilitating the formation of YBCO in 30 min instead of 12+ h. Precursor selection plays an important role in tuning the thermodynamics of interfacial reactions and emerges as an important design parameter in planning kinetically favorable synthesis pathways to complex ceramic materials.

Formation Mechanism of ß-Li3PS4 through Decomposition of Complexes.

ß-Li3PS4 is a solid electrolyte with high Li+ conductivity, applicable to sulfide-based all-solid-state batteries. While a ß-Li3PS4-synthesized by solid-state reaction forms only in a narrow 300-450 °C temperature range upon heating, ß-Li3PS4 is readily available by liquid-phase synthesis through low-temperature thermal decomposition of complexes composed of PS43- and various organic solvents. However, the conversion mechanism of ß-Li3PS4 from these complexes is not yet understood. Herein, we proposed the synthesis mechanism of ß-Li3PS4 from Li3PS4·acetonitrile (Li3PS4·ACN) and Li3PS4·1,2-dimethoxyethane (Li3PS4·DME), whose structural similarity with ß-Li3PS4 would reduce the nucleation barrier for the formation of ß-Li3PS4. Synchrotron X-ray diffraction clarified that both complexes possess similar layered structures consisting of alternating Li2PS4- and Li+-ACN/DME layers. ACN/DME was removed from these complexes upon heating, and rotation of the PS4 tetrahedra induced a uniaxial compression to form the ß-Li3PS4 framework.

Ultrahigh-Pressure Preparation and Catalytic Activity of MOF-Derived Cu Nanoparticles.

A metal-organic framework (MOF) consisting of Cu-benzenetricarboxylic acid was processed under ultrahigh pressure (5 GPa) and at temperature of up to 500 °C. The products were characterized with TEM, FTIR, and XAFS. The decomposition of the MOF started at 200 °C at 5 GPa. This temperature was much lower than that in the vacuum. Single-nanometer Cu nanoparticles were obtained in carbon matrix, which was significantly smaller than the Cu particles prepared at ambient pressure. The catalytic activity for Huisgen cycloaddition was examined, and the sample processed at 5 GPa showed a much improved performance compared with that of the MOF-derived Cu nanoparticles prepared without high pressure.

Evolution of two bulk-superconducting phases in Sr0.5RE0.5FBiS2 (RE: La, Ce, Pr, Nd, Sm) by external hydrostatic pressure effect.

Polycrystalline samples of Sr0.5RE0.5FBiS2 (RE: La, Ce, Pr, Nd, and Sm) were synthesized via the solid-state reaction and characterized using synchrotron X-ray diffraction. Although all the Sr0.5RE0.5FBiS2 samples exhibited superconductivity at transition temperatures (Tc) within the range of 2.1-2.7 K under ambient pressure, the estimated superconducting volume fraction was small, which indicates non-bulk nature of superconductivity in those samples under ambient pressure. A dramatic increase in shielding fraction, which indicates the emergence of the bulk superconductivity was achieved by applying external hydrostatic pressures. We found that two phases, low-P phases with Tc = 2.5-2.8 K and high-P phases with Tc = 10.0-10.8 K, were induced by the pressure effect for samples with RE = La, Ce, Pr, and Nd. Pressure-Tc phase diagrams indicated that the critical pressure for the emergence of the high-P phase tends to increase with decreasing ionic radius of the doped RE ions, which was explained by the correlation between external and chemical pressure effects. According to the high-pressure X-ray diffraction measurements of Sr0.5La0.5FBiS2, a structural phase transition from tetragonal to monoclinic also occurred at approximately 1.1 GPa. Bulk superconducting phases in Sr0.5RE0.5FBiS2 induced by the external hydrostatic pressure effect are expected to be useful for understanding the effects of both external and chemical pressures to the emergence of bulk superconductivity and pairing mechanisms in BiCh2-based superconductors.

Growth and Characterization of ROBiS2 High-Entropy Superconducting Single Crystals.

A series of high-entropy superconductors, ROBiS2 (R = La + Ce + Pr + Nd + Sm), have been successfully grown in the form of single crystals using CsCl flux. The obtained single crystals have a platelike shape with a size of 0.5-2.0 mm and a thickness of 70-450 µm, and they are cleavable along the c-plane. The c-axis lattice constants of the obtained ROBiS2 single crystals have similar values of 13.47-13.57 Å. The Ce in the obtained ROBiS2 single crystals was in a mixed-valence state, comprising both Ce3+ and Ce4+. On the other hand, Pr and Sm showed only the trivalent state. The superconducting transition temperatures of ROBiS2 single crystals were approximately 2-4 K. The superconducting transition temperature and superconducting anisotropies of R-site mixed high-entropy samples increased with a decrease in the mean ionic radius of the R-site. Moreover, a deviation in the tendency to exhibit superconducting properties was observed based on the difference in the R-site mixed entropy. R-site mixed entropy in ROBiS2 superconductors may affect their superconducting properties.

Timing of Nutrient Ingestion after Mild to Moderate Cycling Exercise Does Not Affect Gastric Emptying Rate in Humans.

This study examined the effect of carbohydrate drink ingestion timing on gastrointestinal tract blood flow and motility after mild cycling exercise. Eight healthy participants were randomly assigned to ingest a liquid solution with 75 g glucose at either 5 min (PE-5) or 30 min (PE-30) after a single bout of leg cycling exercise according to target heart rate (approximately 120 beats/min). As the control trial (Con), participants ingested the same liquid solution without exercise. Celiac artery blood flow (BF), superior mesenteric artery BF, and gastric emptying rate were assessed by ultrasonography before and for 60 min after ingesting the glucose solution. Blood lactate, glucose, and plasma insulin were also measured at baseline and for 60 min after ingesting the glucose solution. Celiac artery BF significantly decreased from resting baseline immediately after exercise in both the PE-5 and PE-30 trials, and then returned to resting baseline just before the ingestion of glucose solution in the PE-30 trial. After ingesting the glucose solution, changes in celiac artery BF, superior mesenteric artery BF, % gastric emptying rate, blood lactate, blood glucose, and plasma insulin were not significantly different among the three trials. The timing of nutrient ingestion after mild exercise does not seem to impact the subsequent gastrointestinal motility, blood flow, and glycemic responses.